Disperse dye mixtures, their preparation and use

ABSTRACT

The present invention provides dye mixtures containing at least one dye of formula (I) and at least one dye of formula (II) where T 1 , T 2 , R 1  to R 9  and n are each as defined in claim  1 , processes for their preparation and their use.

The present invention relates to disperse dyes for dyeing hydrophobictextile materials.

Mixtures of benzodifuranone and disperse azo dyes are already known andare described for example in EP 0 305 886 A2, EP 0 640 667 A1 andWO2008/074719 A1.

In addition, WO2008/049758 A2 discloses disperse azo dyes in which a2-oxoalkyl ester is linked to the chromophore.

It has now been found that the hereinbelow defined mixtures ofbenzodifuranone and disperse azo dyes are distinctly improved over theindividual dyes in respect of the buildup of the dyeings on polyesterand polyester-elastane materials.

The present invention provides dye mixtures containing at least one dyeof formula (I)

and at least one dye of formula (II)

where

-   T¹ is hydrogen, halogen, trifluoromethyl, cyano, —SCN, —SO₂CH₃ or    nitro;-   T² is hydrogen or halogen;-   R¹ is hydrogen, (C₁-C₆)-alkyl, (C₁-C₄)-alkoxy, halogen, —NHCHO,    —NHCO(C₁-C₆)-alkyl, —NHCOaryl, —NHSO₂(C₁-C₆)-alkyl or —NHSO₂aryl;-   R² is hydrogen or halogen;-   R³ is hydrogen, (C₁-C₆)-alkyl, cyano-, (C₁-C₄)-alkoxy-, phenoxy- or    phenyl-substituted (C₁-C₆)-alkyl, (C₃-C₄)-alkenyl or substituted    (C₃-C₄)-alkenyl;-   R⁴ is hydrogen or methyl;-   R⁵ is methyl or ethyl;-   R⁶ is hydrogen or methyl;-   R⁷ is hydrogen or methyl;-   n is 0, 1, 2 or 3;-   R⁸ and R⁹ are each independently hydrogen, (C₁-C₄)-alkoxy,    (C₂-C₄)-alkenyloxy or −O(CH₂)_(q)R²²; and-   q is an integer from 1 to 6; and-   R²² is 2-tetrahydropyranyl, 2-tetrahydrofuranyl, —OR²³ or —COR²⁴;    where-   R²³ is hydrogen, (C₁-C₄)-alkyl, (C₂-C₄)-alkenyl, substituted or    unsubstituted phenyl, (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl,    phenoxy-(C₁-C₄)-alkyl, carbonyl-(C₁-C₄)-alkyl,    carbonyl-(C₂-C₄)-alkenyl, carbonyl phenyl,    carbonyl-(C₁-C₄)-alkoxy-(C₂-C₄)-alkyl or    carbonylphenoxy-(C₂-C₄)-alkyl; and-   R²⁴ is (C₁-C₄)-alkoxy, (C₂-C₄)-alkenyloxy, substituted or    unsubstituted phenyloxy, phenyl-(C₁-C₂)-alkoxy,    phenoxy-(C₁-C₄)-alkoxy, (C₂-C₄)-alkenyloxy-(C₁-C₄)-alkoxy or    (C₁-C₄)-alkoxy-(C₁-C₄)-alkoxy.

In the context of the present invention, (C₁-C₆)-alkyl groups may bestraight chain or branched and are for example methyl, ethyl, n-propyl,i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or n-hexyl. A similarlogic holds for alkoxy groups, which are methoxy or ethoxy for example.(C₃-C₄)-Alkenyl groups are more particularly allyl, (C₂-C₄)-alkenylgroups are more particularly vinyl or allyl.

Substituents for (C₃-C₄)-alkenyl are for example halogen and phenyl.

Aryl is more particularly phenyl or naphthyl. Substituents for phenyl orphenoxy are for example halogen, methyl, ethyl, hydroxyethyl, methoxy,ethoxy, hydroxyl and cyano.

—NHSO₂aryl is more particularly phenylsulfonylamino. Halogen ispreferably chlorine or bromine.

Preferred dye mixtures according to the present invention contain atleast one dye of formula (I) where

-   T¹ is hydrogen, chlorine, bromine, trifluoromethyl, cyano or nitro;-   T² is hydrogen or chlorine;-   R¹ is hydrogen, chlorine, methyl, acetylamino, propionylamino,    benzoylamino; methylsulfonylamino, ethylsulfonylamino or    phenylsulfonylamino;-   R² is hydrogen or chlorine;-   R³ is hydrogen, methyl, ethyl, propyl, butyl, benzyl, phenylethyl,    phenoxyethyl, methoxyethyl, cyanoethyl or allyl;-   R⁴, R⁶ and R⁷ are each hydrogen;-   R⁵ is methyl; and-   n is 0 or 1.

Particularly preferred dye mixtures according to the present inventioncontain at least one dye of formula (I) where

-   T¹ is hydrogen, chlorine, bromine, trifluoromethyl, cyano or nitro;-   T² is hydrogen or chlorine;-   R¹ is hydrogen, methyl or acetylamino;-   R² is hydrogen or chlorine;-   R³ is hydrogen, methyl, ethyl, n-butyl, benzyl, phenylethyl,    phenoxyethyl, cyanoethyl or allyl;-   R⁴, R⁶ and R⁷ are each hydrogen;-   R⁵ is methyl; and-   n is 0.

Very particularly preferred dye mixtures according to the presentinvention contain at least one dye of formula (Ia)

where T¹, T² and R¹ to R³ are each as defined in the table whichfollows:

T¹ T² R¹ R² R³ Ia-1 Cl H NHCOCH₃ H n-C₄H₉ Ia-2 H H NHCOCH₃ H n-C₄H₉ Ia-3NO₂ H NHCOCH₃ H CH₂CH₃ Ia-4 CN H NHCOCH₃ H CH₂CH₃ Ia-5 Cl H NHCOCH₃ HCH₂CH₃ Ia-6 Br H NHCOCH₃ H CH₂CH₃ Ia-7 H H NHCOCH₃ H CH₂CH₃ Ia-8 CN HNHCOCH₃ H CH₂C₆H₅ Ia-9 Cl H NHCOCH₃ H CH₂C₆H₅ Ia-10 NO₂ H NHCOCH₃ HCH₂C₆H₅ Ia-11 H H NHCOCH₃ H CH₂C₆H₅ Ia-12 CN H NHCOCH₃ H n-C₄H₉ Ia-13 CNH NHCOCH₃ H CH₂CH═CH₂ Ia-14 Cl H NHSO₂CH₃ H CH₂C₆H₅ Ia-15 H H NHSO₂CH₃ HCH₂C₆H₅ Ia-16 CN H CH₃ H CH₂CH₃ Ia-17 CN H CH₃ H n-C₄H₉ Ia-18 Cl H CH₃ Hn-C₄H₉ Ia-19 Cl H CH₃ H CH₂CH₃ Ia-20 Cl H H H CH₂CH₃ Ia-21 Br H H HCH₂CH₃ Ia-22 Cl Cl H H CH₂CH₃ Ia-23 Cl H H H CH₂C₆H₅ Ia-24 CN H H HCH₂C₆H₅ Ia-25 CF₃ H H H CH₂C₆H₅ Ia-26 Br H H H CH₂C₆H₅ Ia-27 CN H H HCH₂CH₂OC₆H₅ Ia-28 H H CH₃ H CH₂CH₃ Ia-29 Br H CH₃ H CH₂CH₃ Ia-30 Cl ClCH₃ H CH₂CH₃ Ia-31 Cl Cl H H CH₂C₆H₅ Ia-32 H H H Cl H Ia-33 Cl H H Cl HIa-34 H H H Cl H Ia-35 NO₂ H NHCOCH₃ Cl H Ia-36 H H NHCOCH₃ Cl H Ia-37Cl H NHCOCH₃ Cl H Ia-38 CN H NHCOCH₃ Cl H Ia-39 CN H H H CH₂CH₂CN Ia-40CF₃ H H H CH₂CH₂CN Ia-41 Cl H H H CH₂CH₂CN Ia-42 CN H CH₃ H CH₂CH₂CNIa-43 CN H CH₃ Cl CH₂CH₂CN Ia-44 CF₃ H H Cl H Ia-45 CN H H Cl H Ia-46CF₃ H NHCOCH₃ Cl H Ia-47 Cl H H H CH₂CH₂C₆H₅ Ia-48 CN H H H CH₂CH₂C₆H₅Ia-49 NO₂ H H H CH₂C₆H₅

Further preferred dye mixtures according to the present inventioncontain at least one dye of formula (II) where

R⁸ and R⁹ are each independently hydrogen, (C₁-C₄)-alkoxy or—O(CH₂)_(q)R²² whereq is an integer from 1 to 3; andR²² is 2-tetrahydropyranyl, 2-tetrahydrofuranyl, —OR²³ or —COR²⁴; whereR²³ is hydrogen or (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl; andR²⁴ is (C₁-C₄)-alkoxy-(C₁-C₄)-alkoxy.

Further particularly preferred dye mixtures according to the presentinvention contain at least one dye of formula (II) where

R⁸ is hydrogen, (C₁-C₄)-alkoxy or —O(CH₂)_(q)R²², whereq is an integer from 1 to 3; andR²² is 2-tetrahydropyranyl, 2-tetrahydrofuranyl, —OR²³ or —COR²⁴; whereR²³ is hydrogen or (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl; andR²⁴ is (C₁-C₄)-alkoxy-(C₁-C₄)-alkoxy;andR⁹ is hydrogen, (C₁-C₄)-alkoxy or —O(CH₂)_(q)R²², whereq is an integer from 1 to 3; and

R²² is —COR²⁴ and

R²⁴ is (C₁-C₄)-alkoxy-(C₁-C₄)-alkoxy.

Further very particularly preferred dye mixtures according to thepresent invention contain at least one dye of formula (II) where R⁸ andR⁹ are each as defined in the table which follows and * represents thebond to the phenyl radical:

R⁸ R⁹ II-1 H

II-2

II-3

H II-4

H II-5

H II-6

H II-7

H II-8

H II-9

H II-10

H II-11

II-12

Very particularly preferred dye mixtures according to the presentinvention contain the dyes of formulae Ia-11, Ia-23, Ia-24 and/or Ia-25together with the dyes of formulae II-1, II-2, II-3, II-8 and/or II-1.

Dye mixtures according to the present invention which contain the dye offormula Ia-24 and the dye of formula II-3 are more particularlypreferred.

The dye mixtures according to the present invention contain the dyes offormulae (I) and (II) more particularly in amounts each from 1% to 99%by weight, more preferably in amounts of in each case 20% to 80% byweight. Very particularly preferred dye mixtures according to thepresent invention contain dyes of formula (I) in amounts from 30% to 45%by weight and dyes of formula (II) in amounts from 55% to 70% by weight.

Suitable mixing ratios for dye of formula (I):dye of formula (II) are90:10, 80:20, 75:25, 70:30, 60:40, 55:45, 50:50, 45:55, 40:60, 30:70,25:75, 20:80 and 10:90.

The dye mixtures according to the present invention are obtainable bymechanically mixing the dyes of formulae (I) and (II). The amounts aremore particularly chosen so as to produce mixtures having the desiredcompositions.

The dyes of formula (I) are known and are described for example inWO2008/049758. Similarly, the dyes of formula (II) are known anddescribed for example in EP 0 033 583 A1 and EP 0 397 170 A1.

The dye mixtures according to the present invention are very useful fordyeing and printing hydrophobic materials in that the dyeings and printsobtained are notable for level shades and high service fastnesses.Deserving of particular mention are good wash and contact fastnesses andalso excellent color buildup properties, especially on polyester andpolyester-elastane materials.

The present invention thus also provides for the use of the dye mixturesof the present invention for dyeing and printing hydrophobic materials,i.e., processes for dyeing or printing such materials in a conventionalmanner wherein a dye mixture according to the present invention is usedas a colorant.

The hydrophobic materials mentioned can be of synthetic or semisyntheticorigin. Examples include secondary cellulose acetate, cellulosetriacetate, polyamides, polylactides and more particularly highmolecular weight polyesters. Materials composed of high molecular weightpolyester are more particularly those based on polyethyleneterephthalates or polytrimethylene terephthalates. Blend fabrics andblend fibers such as for example polyester-cotton or polyester-elastaneare also possible. The hydrophobic synthetic materials can be present inthe form of self-supporting film/sheeting or fabric- or thread-shapedbodies and may for example have been processed into yarns or woven orknitted textile fabrics. Preference is given to fibrous textilematerials, which may also be present in the form of microfibers forexample.

The dyeing in accordance with the use provided by the present inventioncan be effected in a conventional manner, preferably from an aqueousdispersion, if appropriate in the presence of carriers, at between 80 toabout 110° C. by the exhaust process or in a dyeing autoclave at 110 to140° C. by the HT process, and also by the so-called thermofix process,in which the fabric is padded with the dyeing liquor and subsequentlyfixed/set at about 180 to 230° C.

Printing of the materials mentioned can be carried out in a manner knownper se by incorporating the dye mixtures of the present invention in aprint paste and treating the fabric printed therewith at temperaturesbetween 180 to 230° C. with HT steam, high-pressure steam or dry heat,if appropriate in the presence of a carrier, to fix the dye.

The dye mixtures of the present invention shall be in a very fine stateof subdivision when they are used in dyeing liquors, padded liquors orprint pastes. The dyes are converted into the fine state of subdivisionin a conventional manner by slurrying them together with dispersants ina liquid medium, preferably water, and subjecting the mixture to theaction of shearing forces to mechanically comminute the originallypresent dye particles to such an extent that an optimal specific surfacearea is achieved and sedimentation of the dye is minimized. This isaccomplished in suitable mills, such as ball or sand mills. The particlesize of the dyes is generally between 0.5 and 5 μm, and preferably equalto about 1 μm.

The dispersants used in the milling operation can be nonionic oranionic. Nonionic dispersants are for example reaction products ofalkylene oxides, for example ethylene oxide or propylene oxide, withalkylatable compounds, for example fatty alcohols, fatty amines, fattyacids, phenols, alkylphenols and carboxamides. Anionic dispersants arefor example lignosulfonates, alkyl- or alkylarylsulfonates or alkylarylpolyglycol ether sulfates.

The dye preparations thus obtained shall be pourable for mostapplications. Accordingly, the dye and dispersant content is limited inthese cases. In general, the dispersions are adjusted to a dye contentof up to 50 percent by weight and a dispersant content of up to about 25percent by weight. For economic reasons, dye contents are in most casesnot below 15 percent by weight. The dispersions may also contain stillfurther auxiliaries, for example those which act as an oxidizing agent,for example sodium m-nitrobenzenesulfonate, or fungicidal agents, forexample sodium o-phenylphenoxide and sodium pentachlorophenoxide, andparticularly so-called “acid donors”, examples being butyrolactone,monochloroacetamide, sodium chloroacetate, sodium dichloroacetate, thesodium salt of 3-chloropropionic acid, monosulfate esters such as laurylsulfate for example, and also sulfuric esters of ethoxylated andpropoxylated alcohols, for example butylglycol sulfate.

The dye dispersions thus obtained are very advantageous for making updyeing liquors and print pastes.

There are certain fields of use where powder formulations are preferred.These powders contain the dye, dispersants and other auxiliaries, forexample wetting, oxidizing, preserving and dustproofing agents and theabovementioned “acid donors”.

A preferred method of making pulverulent dye preparations consists instripping the above-described liquid dye dispersions of their liquid,for example by vacuum drying, freeze drying, by drying on drum dryers,but preferably by spray drying.

The dyeing liquors are made by diluting the requisite amounts of theabove-described dye formulations with the dyeing medium, preferablywater, such that a liquor ratio of 5:1 to 50:1 is obtained for dyeing.In addition, it is generally customary to add further dyeingauxiliaries, such as dispersing, wetting and fixing auxiliaries, to theliquors. Organic and inorganic acids such as acetic acid, succinic acid,boric acid or phosphoric acid are added to set a pH in the range from 4to 5, preferably 4.5. It is advantageous to buffer the pH setting and toadd a sufficient amount of a buffering system. The acetic acid/sodiumacetate system is an example of an advantageous buffering system.

To use the dye mixture in textile printing, the requisite amounts of theabovementioned dye formulations are kneaded in a conventional mannertogether with thickeners, for example alkali metal alginates or thelike, and optionally further additives, for example fixationaccelerants, wetting agents and oxidizing agents, to give print pastes.

The present invention also provides inks for digital textile printing bythe ink jet process, said inks containing a dye mixture according to thepresent invention.

The inks of the present invention are preferably aqueous and contain dyemixtures of the present invention in amounts ranging for example from0.1% to 50% by weight, preferably in amounts ranging from 1% to 30% byweight and more preferably in amounts ranging from 1% to 15% by weightbased on the total weight of the ink. They further contain moreparticularly from 0.1% to 20% by weight of a dispersant. Suitabledispersants are known to a person skilled in the art, are commerciallyavailable and include for example sulfonated or sulfomethylated lignins,condensation products of aromatic sulfonic acids and formaldehyde,condensation products of optionally substituted phenol and formaldehyde,polyacrylates and corresponding copolymers, modified polyurethanes andreaction products of alkylene oxides with alkylatable compounds, forexample fatty alcohols, fatty amines, fatty acids, carboxamides andoptionally substituted phenols.

The inks according to the present invention may further contain thecustomary additives, for example viscosity moderators to set viscositiesin the range from 1.5 to 40.0 mPas in the temperature range from 20 to50° C. Preferred inks have a viscosity in the range from 1.5 to 20 mPasand particularly preferred inks have a viscosity in the range from 1.5to 15 mPas.

Suitable viscosity moderators are rheological additives, for examplepolyvinyl caprolactam, polyvinylpyrrolidone and also their copolymers,polyetherpolyol, associative thickeners, polyurea, sodium alginates,modified galactomannans, polyetherurea, polyurethane and nonioniccellulose ethers.

By way of further additions, the inks according to the present inventionmay contain surface-active substances to set surface tensions in therange from 20 to 65 mN/m, which are adapted as appropriate depending onthe process used (thermal or piezo technology).

Suitable surface-active substances are for example surfactants of anykind, preferably nonionic surfactants, butyldiglycol and 1,2-hexanediol.

The inks may further contain customary additions, for example substancesto inhibit fungal and bacterial growth in amounts from 0.01% to 1% byweight based on the total weight of the ink.

The inks according to the present invention are obtainable in aconventional manner by mixing the components in water.

EXAMPLE 1

a) 50 parts of the dye (Ia-24)

are mechanically mixed with 50 parts of the dye (II-3)

Then, the mixture is ground as a 40% aqueous suspension with 100 partsof a high temperature stable dispersant until the particle size(diameter) has reached the size magnitude of 0.1-5 micrometers.

This dispersion is standardized to a solid product containing 25% of thedye mixture and 70% dispersant, by adding 99.7 parts of a “cuttingagent” and by drying in a spray dryer either in powder form.

b) 2 g of the dye mixture obtained as per a) are dispersed in 100 ml ofwater at 40-50° C. A dyebath is prepared from 11.5 ml of this aqueousdispersion, 57.5 ml of deionized water and 1.2 ml of buffering solution(pH 4.5) and entered with a 5 g piece of polyester. The dyebath isheated to 130° C. and maintained at 130° C. for 45 minutes in a WernerMathis high temperature dyeing machine. After rinsing with water andreduction clearing, the polyester material has a ruby red hue havingexcellent wash fastnesses. A particularly interesting property of thismixture is the excellent buildup behavior on polyester and polyestermicrofiber. Polyester microfiber requires proportionally more of themixture to achieve a comparable depth of shade to conventionalpolyester.

Example 1 is repeated in similar fashion to obtain the dye mixtures ofexamples 2 to 20 according to the invention and use them for dyeingpolyester. The table which follows indicates the fraction of therespective dye in % by weight based on the total dye content.

Dye Example Ia-11 Ia-23 Ia-24 Ia-25 II-1 II-2 II-3 II-8 II-10 2 30 70 330 70 4 25 25 25 25 5 20 20 60 6 50 50 7 30 10 40 20 8 48 52 9 60 40 1080 20 11 33 67 12 46 54 13 44 56 14 44 31 14 11 15 34 33 33 16 30 35 3517 30 35 35 18 40 60 19 40 10 10 10 20 20 10 70

EXAMPLE 21

A textile fabric consisting of polyester is pad-mangled with the liquorconsisting of 50 g/l of 8% sodium alginate solution, 100 g/l of an 8-12%carob flour ether solution and 5 g/l of mononsodium phosphate in waterand then dried. The wet pickup is 70%. The textile thus pretreated isprinted with an aqueous ink prepared in accordance with the proceduredescribed above and containing

3.5% of the dye of example 1,2.5% of Disperbyk 190 dispersant,30% of 1,5-pentanediol,5% of diethylene glycol monomethyl ether,0.01% of Mergal K9N biocide and58.99% of waterusing a drop-on-demand (piezo) ink jet print head. The print is fullydried. Fixing is effected by means of superheated steam at 175° C. for 7minutes. The print is subsequently subjected to an alkaline reductionclear, rinsed warm and then dried.

1-10. (canceled)
 11. A dye mixture containing at least one dye offormula (I)

and at least one dye of formula (II)

where T¹ is hydrogen, halogen, trifluoromethyl, cyano, —SCN, —SO₂CH₃ ornitro; T² is hydrogen or halogen; R¹ is hydrogen, (C₁-C₆)-alkyl,(C₁-C₄)-alkoxy, halogen, —NHCHO, —NHCO(C₁-C₆)-alkyl, —NHCOaryl,—NHSO₂(C₁-C₆)-alkyl or —NHSO₂aryl; R² is hydrogen or halogen; R³ ishydrogen, (C₁-C₆)-alkyl, cyano-, (C₁-C₄)-alkoxy-, phenoxy- orphenyl-substituted (C₁-C₆)-alkyl, (C₃-C₄)-alkenyl or substituted(C₃-C₄)-alkenyl; R⁴ is hydrogen or methyl; R⁵ is methyl or ethyl; R⁶ ishydrogen or methyl; R⁷ is hydrogen or methyl; n is 0, 1, 2 or 3; R⁸ andR⁹ are each independently hydrogen, (C₁-C₄)-alkoxy, (C₂-C₄)-alkenyloxyor —O(CH₂)_(q)R²²; and q is an integer from 1 to 6; and R²² is2-tetrahydropyranyl, 2-tetrahydrofuranyl, —OR²³ or —COR²⁴; where R²³ ishydrogen, (C₁-C₄)-alkyl, (C₂-C₄)-alkenyl, substituted or unsubstitutedphenyl, (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl, phenoxy-(C₁-C₄)-alkyl,carbonyl-(C₁-C₄)-alkyl, carbonyl-(C₂-C₄)-alkenyl, carbonylphenyl,carbonyl-(C₁-C₄)-alkoxy-(C₂-C₄)-alkyl or carbonylphenoxy-(C₂-C₄)-alkyl;and R²⁴ is (C₁-C₄)-alkoxy, (C₂-C₄)-alkenyloxy, substituted orunsubstituted phenyloxy, phenyl-(C₁-C₂)-alkoxy, phenoxy-(C₁-C₄)-alkoxy,(C₂-C₄)-alkenyloxy-(C₁-C₄)-alkoxy or (C₁-C₄)-alkoxy-(C₁-C₄)-alkoxy. 12.The dye mixture as claimed in claim 11, wherein T¹ is hydrogen,chlorine, bromine, trifluoromethyl, cyano or nitro; T² is hydrogen orchlorine; R¹ is hydrogen, chlorine, methyl, acetylamino, propionylamino,benzoylamino; methylsulfonylamino, ethylsulfonylamino orphenylsulfonylamino; R² is hydrogen or chlorine; R³ is hydrogen, methyl,ethyl, propyl, butyl, benzyl, phenylethyl, phenoxyethyl, methoxyethyl,cyanoethyl or allyl; R⁴, R⁶ and R⁷ are each hydrogen; R⁵ is methyl; andn is 0 or
 1. 13. The dye mixture as claimed in claim 11, wherein T¹ ishydrogen, chlorine, bromine, trifluoromethyl, cyano or nitro; T² ishydrogen or chlorine; R¹ is hydrogen, methyl or acetylamino; R² ishydrogen or chlorine; R³ is hydrogen, methyl, ethyl, n-butyl, benzyl,phenylethyl, phenoxyethyl, cyanoethyl or allyl; R⁴, R⁶ and R⁷ are eachhydrogen; R⁵ is methyl; and n is
 0. 14. The dye mixture as claimed inclaim 11, containing at least one dye of formula (Ia)

where T¹, T² and R¹ to R³ are each as defined in the table whichfollows: T¹ T² R¹ R² R³ Ia-1 Cl H NHCOCH₃ H n-C₄H₉ Ia-2 H H NHCOCH₃ Hn-C₄H₉ Ia-3 NO₂ H NHCOCH₃ H CH₂CH₃ Ia-4 CN H NHCOCH₃ H CH₂CH₃ Ia-5 Cl HNHCOCH₃ H CH₂CH₃ Ia-6 Br H NHCOCH₃ H CH₂CH₃ Ia-7 H H NHCOCH₃ H CH₂CH₃Ia-8 CN H NHCOCH₃ H CH₂C₆H₅ Ia-9 Cl H NHCOCH₃ H CH₂C₆H₅ Ia-10 NO₂ HNHCOCH₃ H CH₂C₆H₅ Ia-11 H H NHCOCH₃ H CH₂C₆H₅ Ia-12 CN H NHCOCH₃ Hn-C₄H₉ Ia-13 CN H NHCOCH₃ H CH₂CH═CH₂ Ia-14 Cl H NHSO₂CH₃ H CH₂C₆H₅Ia-15 H H NHSO₂CH₃ H CH₂C₆H₅ Ia-16 CN H CH₃ H CH₂CH₃ Ia-17 CN H CH₃ Hn-C₄H₉ Ia-18 Cl H CH₃ H n-C₄H₉ Ia-19 Cl H CH₃ H CH₂CH₃ Ia-20 Cl H H HCH₂CH₃ Ia-21 Br H H H CH₂CH₃ Ia-22 Cl Cl H H CH₂CH₃ Ia-23 Cl H H HCH₂C₆H₅ Ia-24 CN H H H CH₂C₆H₅ Ia-25 CF₃ H H H CH₂C₆H₅ Ia-26 Br H H HCH₂C₆H₅ Ia-27 CN H H H CH₂CH₂OC₆H₅ Ia-28 H H CH₃ H CH₂CH₃ Ia-29 Br H CH₃H CH₂CH₃ Ia-30 Cl Cl CH₃ H CH₂CH₃ Ia-31 Cl Cl H H CH₂C₆H₅ Ia-32 H H H ClH Ia-33 Cl H H Cl H Ia-34 H H H Cl H Ia-35 NO₂ H NHCOCH₃ Cl H Ia-36 H HNHCOCH₃ Cl H Ia-37 Cl H NHCOCH₃ Cl H Ia-38 CN H NHCOCH₃ Cl H Ia-39 CN HH H CH₂CH₂CN Ia-40 CF₃ H H H CH₂CH₂CN Ia-41 Cl H H H CH₂CH₂CN Ia-42 CN HCH₃ H CH₂CH₂CN Ia-43 CN H CH₃ Cl CH₂CH₂CN Ia-44 CF₃ H H Cl H Ia-45 CN HH Cl H Ia-46 CF₃ H NHCOCH₃ Cl H Ia-47 Cl H H H CH₂CH₂C₆H₅ Ia-48 CN H H HCH₂CH₂C₆H₅ Ia-49 NO₂ H H H CH₂C₆H₅


15. The dye mixture as claimed in claim 11, wherein R⁸ and R⁹ are eachindependently hydrogen, (C₁-C₄)-alkoxy or —O(CH₂)_(q)R²² where q is aninteger from 1 to 3; and R²² is 2-tetrahydropyranyl,2-tetrahydrofuranyl, —OR²³ or —COR²⁴; where R²³ is hydrogen or(C₁-C₄)-alkoxy-(C₁-C₄)-alkyl; and R²⁴ is (C₁-C₄)-alkoxy-(C₁-C₄)-alkoxy.16. The dye mixture as claimed in claim 11, wherein R⁸ is hydrogen,(C₁-C₄)-alkoxy or —O(CH₂)_(q)R²², where q is an integer from 1 to 3; andR²² is 2-tetrahydropyranyl, 2-tetrahydrofuranyl, —OR²³ or —COR²⁴; whereR²³ is hydrogen or (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl; and R²⁴ is(C₁-C₄)-alkoxy-(C₁-C₄)-alkoxy; and R⁹ is hydrogen, (C₁-C₄)-alkoxy or—O(CH₂)_(q)R²², where q is an integer from 1 to 3; and R²² is —COR²⁴ andR²⁴ is (C₁-C₄)-alkoxy-(C₁-C₄)-alkoxy.
 17. The dye mixture as claimed inclaim 11, wherein R⁸ and R⁹ are each as defined in the table whichfollows and * represents the bond to the phenyl radical: R⁸ R⁹ II-1 H

II-2

II-3

H II-4

H II-5

H II-6

H II-7

H II-8

H II-9

H II-10

H II-11

II-12


18. The dye mixture as claimed in claim 14, wherein R⁸ and R⁹ are eachas defined in the table which follows and * represents the bond to thephenyl radical: R⁸ R⁹ II-1 H

II-2

II-3

H II-4

H II-5

H II-6

H II-7

H II-8

H II-9

H II-10

H II-11

II-12


19. The dye mixture as claimed in claim 11, containing the dyes offormulae Ia-11, Ia-23, Ia-24 and/or Ia-25 together with the dyes offormulae II-1, II-2, II-3, II-8 and/or II-1.
 20. A process for dyeingand printing hydrophobic material which comprises contacting thematerial with the dye mixture as claimed in claim
 11. 21. An ink fordigital textile printing by the ink jet process, comprising the dyemixture as claimed in claim 11.